Process for the coloration of polyethylene terephthalate textile materials



United States Patent '0 3,154,457 PROES S Fill? 'iHE CGLGRATIQN SF POLY-ETHYL- ENE TEREPHTHALA'IE TEXZHELE MATERIALS Alistair Howard Bernie, Harold Seaman, and Raymond Windle, all of Manchester, England, assignors to limperial Chemical industries Limited, London, England,

a corporation of Great Britain No Drawing. Filed Aug. 1, H62, Ser. No. 213,962 lairns priority, application Great Britain, Aug. 28, 1951,

33,932 6 (Ilairns. (Cl. 8-41) This invention relates to a coloration process and more particularly it relates to a process for the coloration of aromatic polyester textile materials with water-insoluble dyestuffs.

As an example of a polyester textile material there may bementioned polyethylene terephthalate. Such material may be in any desired form, for example threads, yarn or woven or knitted fabric.

By water-insoluble azo dyestuffs is meant, as will be understood by those skilled in the art, dyestuffs which are free from water-solubilising groups. Water solubilising groups which are typically present in water-soluble azo dyestuffs are sulphonic acid, and acyl sulphonamido groups. Such Water-solubilising groups are not present in water-insoluble dyestuifs of our invention, It will be recognised, of course, that these water-solubilising groups are all essentially acidic groups, and will form salts if a dyestuff containing the same is placed in an aqueous alkaline medium. Accordingly, it will be understood that the term water-insoluble azo dyestutl is used herein in its conventional sense as meaning that there are no such sulphonic acid, or acyl sulphonarnido groups, or salts of such groups, in the dyestuff molecule.

According to the invention we provide a process for the coloration of aromatic polyester textile material which comprises applying thereto a Water-insoluble dyestuff of the formula:

'=o- N-n 1 A-N=N i 1 1 0 R oN wherein A represents an aromatic radical of the carbocyclic or heterocyclic series, R is hydrogen or a substituted or unsubstituted alkyl, aralkyl. or aryl radical, and R and R may independently represent hydrogen or substituted or unsubstituted alkyl, aralkyl, or aryl radicals or may together represent the atoms necessary to form, with the adjacent nitrogen atom, a heterocyclic ring, provided that the dyestuir is devoid of water-solubilising groups, and provided also that R and R are not both hydrogen when A and R are both phenyl or substituted phenyl radicals, the same or different.

The aromatic radicals represented by A may be of the carbocyclic, for example the benzene or naphthalene series, or of the heteroeyclic, for example the thiazole or benzthiazole series. All such-radicals may carry sub.- stituents other than water-solubilising groups, for example they may carry as substituents halogen atoms such as chlorine or bromine, alkyl groups such as methyl, ethyl, n-propyl or iso-butyl, alkoxy groups such as methoxy,

ethoxy or beta-methoxyethoxy-, acyl groups such as acetyl,

propionyl or n-butyryl, acylamido groups such as acetamido or p-toluene sulphonamido, amino, nitro, cyano, thiocyano, trifiuoromethyl or carboxy groups.

As examples of radicals which may be represented by R and independently represented bytR and R there may be mentioned methyl, ethyl, beta-hydroxyethyl,

gamma-methoxy-ri-propyl, benzyl, phenyl, p-tolyl, p-nitrophenyl, o-methoxyphenyl, p-methoxyphenyl, o-ethoxyphenyl, o-(beta-methoxyethoxy)phenyl. 7

As examples of heterocyclic rings which may be formed by R and R with the adjacent nitrogen atom there may be mentioned piperidine, piperazine, and morpholine.

The Water-insoluble dyestuffs used in the process of the invention may be obtained in conventional manner by diazotising' amines of the formula A-NH and then coupling with coupling components of the 'formula As examples of amines of the formula ANH there may be mentioned aniline, alphaand beta-naphthylamine, Z-aminothiazole, Z-aminobenzthiazole, p-toluidine, pnitroaniline, 2-cyano 4 nitroaniline, 4-aminophenylmethylsulphone, 4-aminobenzenesulphonamide, 4-a1riino- 3-chlorobenzenesulphonamide, 0-, m-, and p-chloroaniline, 2-nitro-4-methylaniline, 2-cyano-4-methylaniline, oani sidine, p-anisidine, 2:5-dimethoxyaniline, 2-methoxy- 4-nit-roaniline, 2-chloro-4-nitroaniline, anthranilic acid, and 4-aminoazobenzene. 4 As examples of'coupling components of the above for mula there may be mentioned 1-phenyl-3-carbamoyl-5-pyrazolone,

3-carb amoyl-5-pyrazolone,

1methyl-3-carbamoyl-5-pyrazolone,

1- (2-methoxyphenyl -3-carbamoyl-5-pyrazolone,

1-phenyl 3- (N-methylcarb amoyl -5-pyraZolone,

1-phenyl-3- (N-ethylcarbamoyl) -5-pyrazolone,

1-phenyl-3- (N N-dimethylcarbamoyl) -5-pyrazo1one,

1-phenyl-3- (N-beta-methoxyethyl-carbamoyl) -5- pyrazo'lone, I p

1-phenyl-3- (N-phenylcarbamoyl) -5-py-razolone,

1-pheriyl-3 (N-meIthyl-N-phenyl-carbamoyl) -5- pyrazolone,

l-phenyl-S- (p-rnethoxyphenylcarbamoyl -5-pyrazolone,

1-phenyl-3- o-methoxyphenylcarbamoyl) -5-pyrazolone,

1-phenyl-3 o- (beta-methoxyethoxy) phenylcarb amoyl 5-pyrazolone and 1- (naphthl yl) -3-carbamoyl-5-pyrazolone.

The process of the invention may be carried out by immersing the aromatic polyester textile material in a dyebath comprising an aqueous dispersion of a Waterinsoluble dyestuff as hereinbefore defined, the dispersion being stabilized if desired by dispersing (agents such as sulphonated naphthalene-formaldehyde condensates. The dyebath may be heated at or near the boiling point, with addition of a carrier such as diphenyl or o-hydroxydiphenyl, or it may be heated above 100 C. in a closed vessel, with or without the addition of a carrier.

Alternatively an aqueous dispersion of the Water-insoluble dyestufi may be padded on to the aromatic poly: es-tertextile material and fixed by baking the material, for example .for 1 to 2 minutes at between and 220 C. The padding liquor may advantageously contain a thickener or migration inhibitor and other additives suchas urea.

If desired, the process of the invention may be carried out by applying to the surface 'of the textile material a thickened printing paste containing an aqueous dispersion of the Water-insoluble dyestuff, and subsequently steain ing or baking. Suitable thickening agents include gum tragacanth, gum arabic, Nafka crystal gum, alginates, or oil-in-water or water-in-oil emulsions. The printing pastemay also contain commonly used adjuvants such as sur Patented Jan. 5, '1 965 a face active agents and sodium m-nitrobenzene sulphonate. After carrying out the process of the invention the textile material may be removed from the dyehath, steamer or baker, rinsed and treated with soap or synthetic deter-- ture of the dyestulfs because much of the pressure dyeing equipment availablein dyehouses will not, with safety,

tures higher than 130 C. The preferred dyestuffs of our invention are outstanding in all fastness properties, particularly in fiastness to washing, to light and to dry heat treatments at the very high temperatures such as are now gent. It is also advantageous to treat the textile mate- 5 used in the pleating of aromatic polyester textile materials. rial witha weak alkaline solution of sodium hydrosulphite In the above formula the halogen atoms representable before soaping, since this helps to remove loosely attached by X and Y may be, for example, chlorine or bromine. dyestufii from the surface of the fibers. The carbalkoxy or carbo (substituted alkoxy) radicals The process of theinvention provides a means whererepresentable by X may be, for example, radicals of the by aromatic polyester textile materials may be coloured 1 formula COOCH COOC H or -COOC H or yellowto red shades of good fastness to washing and carbo (alkoxyalkyl) radicals of the formula (eg. todryheat treatments. -COOC H OCH or -COOC H OC H The alkoxy particular interest. for use the process of the inor substituted alkoxy radicals representable by Z may be, ventiori are the dyestuifs of the formula for example, radicals of the formula -OCH OC H -OC H or alkoxyalkoxy radicals of the formula {c.g.)

7 & oc n,ocn or oc,n,oc n

\ The invention is illustrated but not limited by the fol- 0 lowing examples in which the parts and percentages are by weight.

I D Example 1 wherein Brepresents a radical of the benzene, naphtha- A dyebalh is pl'eparfid y mining 1 1 Of l lene, thiazole or benzthiazole series, E represents a radi- Y- l l -PY With 30 cal ofthe benzene series, F represents hydrogen or a Parts of Water Containing 1 P of the Sodium Salt 0f lower alkyl radical, D represents hydrogen or a lower a formaldehyde-napthalene sulphonic acid condensate and .alkoxyor alkoxyalkoxy, radical and the term lower indiadding The dispersion 50 Obtained to 4,000 Parts Of Water .cates a radical containing not more than 5 carbon atoms. Paris of W Sodium Sulphate 190 Parts On aromatic polyester textile materials such dyestufls 0f polyethl'lenfi terephthalate fabric is Placed in thc y produce yellow to red shades which are fast to w hi bath which is then heated to 130 C. for minutes in t dryheat audio li h 30 a closed vessel. The polyethylene terephthalate textile A di to a f th d Preferred f tur f our material is then rinsed in water and immersed for 15 i ti we id as new compounds, thg waterminutes at 50 C. in an aqueous solution containing insoluble d t fl f the f la; 0.2% of sodium hydroxide, 0.2% of sodium hydrosul- Y phite and 0.1% of cetyl trimethyl ammonium bromide. The polyethylene terephthalate textile material is again OZC rinsed in water and then lmmersed for 15 minutes in a warm aqueous solution of a synthetic detergent, rinsed @1N=N in water and dried. X 0 z The polyethylene terephthalate textile material is dyed 40 a yellow shade with good fastness to heat treatments.

wherein X represents halogen or a lower carbalkoxy or Example 2 'oarbo (substituted alkoxy) radial, Y represents hydro- In place of 3-carbamoyl-4-(2-methoXy-4'-nitrophenylgen or halogen, Z -repre'sents'hydrogen or alower alkoxy azo)-5-pyrazolone in Example 1 there may he used 1- or substituted al-koxy radical, and the term lower indiphenyl 3 (N phenylcarbamoyl) 4 (2' methoxycates a radicalnof not more than 5 carbon atoms. 4-nitrophenylazo)-5-pyrazolone. The polyethylene ter- The dyestuifs forming the preferred feature of our inephthalate textile material is dyed a reddish yellow shade vention have very good affinity for aromatic polyester with good fastness to heat treatments. textile materials andmay satisfactorily be applied at a The following table lists diazo (column 2) and coudyebath temperature of 130 C. This is a valuable feapling (column 3) components which may be coupled to produce dyestulfs suitable for dyeing polyethylene terephthalate textile material by the method described in Exampie 1. The shades of the dyestuffs are given in column 4.

withstand the pressures created by heating to tempera- Shade on Example Diazo Component Coupling Component polyethylene terephthalate l-phenylB-carb amoyl-fi-pyrazolone i Orange. do Reddish yellow.

methylcarbamoyl-S-pyrazolone. Orange.

l-pheuy -3-N-ethylcarbamoyl-5-pyrazolone 1-pheny1-3-N:N-diethylearbarnoyl5-pyrazolone l-phenyl-El-N-(fl-methoxyethyl) carh amoyl-5-pyrazolone. l-phenyl-3-N-methyl-N-phenylcarb amo yl-fi-pyrazolone. l-phenyl-B-N-(4-methoxyphenyl)carbamoyLS-pyrazolona.

1-phenyl-3- N-rnethyl-N-phenylcarbamoyl-E-pyrazolone. 3carbam0yl-5-pyrazolono 1-phenyl-3-N :N-diethylearhamoyl-5-pyrazolone 1-pheuyl-3-\l-(2-methoxyphenyl) carbamoyl-S-pyrazolone Do. Reddish yellow.

0 Yellow. Orange.

l-phenyl-3-N-(2-methoxyphenyl)oarbamcyl-Spyrazolona- Do. 1-phenyl'-3-N-{2-(fl-methoxyethoxy)phenyllcarbamoyl-S-pwazolone. Do. l-methyl-S-carbamoyl-fi-pyrazolone Yellow l-phenyl-B-N-methylcarbamoyl 5-pyrazolone Orange 1-methyl-3-carbamoy1-5-pyrazolone Do l-phenyl-3-N-ethylcarbamoyl-5-pyrazolone Do. 1-pheny1-3-N-[2-(B-methoxyethoxy) phenyllearbamoyH-pyrazolone Do. 1phenyl-3-N-phenylcarbamoyl-5-pyrazolone Do. l-phenyl-tt-N-(B-methoxyethyl) earbamoyl-fi-pyrazolona.. Orange Reddish orange.

Orange.

do ,7 l-phenyl-B-N-[2-[B-methoxyethoxy) phenyl]carbamoyl-fi-pyrazolone] Do. 4,-nitroaniline do Do.

7 textile material which comprises applying thereto a wateri'nsoluble dyestutf of the formula 'alkoxy radicals.

2. A process for the coloration of aromatic polyester textile material which comprises applying thereto l-phenyl 3 N (4-methoxyphenyDcarbamoyl-4-(4"-chlorophenylazo)-5pyrazolone.

'3. A process for the coloration of aromatic polyester textile material which comprises applying thereto l-phenyl- 3 I 4 (4'-methoxyphenyDearbarnoyl-4-(2-chlorophenylaz0)-5-pyrazolone.

4. A process for the coloration of aromatic polyester 8 textile material which comprises applying thereto l-phenyl- 3 N(2'-methoxyphenyDcarbarnoy1-4-[4"-carbo(fiethoxyethoxy)phenylazoI-Spyrazoione.

5. A process for the coloration of aromatic polyester textile material which comprises applying thereto l-phenyi- 3 N phenylcarbarnoyl-4-[4"carho{flethoxyethoxfipherryiazo1-5-pyrazolone.

6. A process for the coloration of aromatic polyester textile material which comprises applying thereto l-phenyl- 3 N-phenylcaroanioyl-4-[3"-carbo(fi-eihoxyethoxykihenylazo}-5 -pyrazolone.

References Cited by the Examiner UNITED STATES PATENTS 2,038,298 4/36 Kiernan et a1 2 0163 2,330,828 10/43 Lubowe et al 260-163 2,898,178 8/59 Kruckenberg 841 2,955,901 10/60 Kruckenherg 84l 3,037,974 6/ 62 Kraclter et al.

3,057,848 13/62 Dehn et al 8-41 X 3,097,197 7/63 Tilley ct al 84l X NORMAN G. TORCHIN, Primary Examiner.

A. LOUIS MONACE-LL, Examiner. 

1. A PROCESS FOR THE COLORATION OF AROMATIC POLYESTER TEXTILE MATERIAL WHICH COMPRISES APPLYING THERETO A WATEINSOLUBLE DYESTUFF OF THE FORMULA 